arXiv subjects

Ivano E. Castelli

Publications and source records attributed to Ivano E. Castelli.

At least 19 recordsLinked to original sources

arXiv2026

A sulfonitride transparent conductive thin film with ultra-high refractive index

With the rise of AI-assisted materials screening, extraordinary properties are now frequently predicted in experimentally uncharted material systems, highlighting the need to develop new synthesis methods for unconventional materials beyond the classic bulk powder form. Here, we establish the first thin-film growth route for any metal sulfonitride compound by realizing Zr2SN2 films with a rare and compelling combination of optical and electrical properties. Zr2SN2 is transparent across most of the visible range while exhibiting a very high average refractive index of 2.95 in the visible, exceeding expectations based on conventional refractive index-bandgap scaling. Importantly, the same Zr2SN2 film shows degenerate n-type conductivity with carrier density above 10^20 cm-3 and intragrain mobility above 8 cm2V-1s-1, approaching those of established transparent conductive oxides. Zr2SN2 thus demonstrates that strong light-matter interaction, optical transparency and electrical conductivity can be reconciled within a single material platform, revealing a new class of high-refractive-index transparent conductors.

cond-mat.mtrl-sci↗

arXiv2026

Designing dislocation-driven polar vortex networks in twisted perovskites

Twisting two atomic layers produces a geometric moire pattern, but bonding-induced interfacial reconstruction fundamentally transforms this into an ordered dislocation network - a distinction obscured in weakly-bonded van der Waals systems. Although in-plane topological vortex nanostructures arising from twisting-induced lateral strain modulation have been linked to periodic moire patterns in freestanding perovskite layers and 2D bilayers, their coupling to the interfacial dislocation network in twisted layers remains unresolved. Here we demonstrate that twisting freestanding SrTiO3 layers undergo interfacial reconstruction into a network of screw dislocations, accompanied by the emergence of in-plane topological vortices. Unlike in previous reports, these vortices are associated with the periodicity of the dislocation network rather than with geometric moire patterns. Four-dimensional scanning transmission electron microscopy (4D-STEM) reveals long-range ordered vortex-antivortex arrays with nearly continuous polarisation rotation. A machine-learning interatomic potential, trained on first-principles calculations, together with phase-field modelling, confirms that competing strains within the dislocation network stabilize polar vortex-antivortex pairs and drive the emergence of an electronic superlattice with a well-defined periodicity. Our results establish twist-controlled dislocation networks as a new and versatile route to designing local polar and electronic structures in oxide materials.

cond-mat.mtrl-sci↗

arXiv2026

AI-enhanced discovery and accelerated synthesis of metal phosphosulfides

Metal phosphosulfides have emerged as unique multifunctional materials, but they present unique synthesis challenges compared to more established material classes such as oxides and nitrides. As a consequence, experimental development and theoretical understanding of phosphosulfides have focused on individual compounds rather than on accelerated broad-range exploration. In this work, we first evaluate the synthesizability and band gaps of 909 hypothetical ternary phosphosulfides by density functional theory. We find 19 previously unknown thermodynamically stable compounds, including the first Si- and Ge-based phosphosulfides. For rapid band gap prediction, we then develop a multi-fidelity machine learning model to translate semilocal density functional theory band gaps into experimentally calibrated band gaps. Importantly, we extend the accelerated material development workflow to the experimental domain by demonstrating a route to high-throughput synthesis and characterization of virtually any phosphosulfide material system. The method is based on thin-film combinatorial libraries and yields over 100 unique compositions in each experiment, enabling us to synthesize four distinct phosphosulfide compounds in only four combinatorial experiments without prior synthesis recipes and without compromising on material quality. Thus, we argue that accelerated materials development workflows combining theory, artificial intelligence, synthesis, and characterization can be viable even for experimentally challenging inorganic materials.

cond-mat.mtrl-sci↗

arXiv2026

Size Dependent Ternary Halide Solid Solutions in Perovskite Nanocrystals

Crystalline solid solutions incorporate guest atoms by substituting host lattice sites up to a solubility limit dictated by solute host similarity. Solid solutions enable tuning various material properties, such as the optoelectronic behavior of halide perovskites. In bulk, incompatibility of Cl:I halide mixtures restricts exploration throughout the ternary halide Cl:Br:I compositional range. However, solubility is extended in nanocrystals which better accommodate a wider range of ions within their lattice. Through high throughput synthesis and spectroscopic characterization of over 3000 samples, along with density functional theory and cluster expansion models, we determine the solubility boundaries of ternary halide perovskite nanocrystals and demonstrate their extended size dependent miscibility. Smaller nanocrystals, with sufficient Br content, stabilize the Cl:Br:I solid solutions, suppress planar stacking fault defects and prevent halide segregation.

cond-mat.mtrl-sci↗

arXiv2025

Implementing a Scalable, Redeployable and Multitiered Repository for FAIR and Secure Scientific Data Sharing: The BIG-MAP Archive

Data sharing in large consortia, such as research collaborations or industry partnerships, requires addressing both organizational and technical challenges. A common platform is essential to promote collaboration, facilitate exchange of findings, and ensure secure access to sensitive data. Key technical challenges include creating a scalable architecture, a user-friendly interface, and robust security and access control. The BIG-MAP Archive is a cloud-based, disciplinary, private repository designed to address these challenges. Built on InvenioRDM, it leverages platform functionalities to meet consortium-specific needs, providing a tailored solution compared to general repositories. Access can be restricted to members of specific communities or open to the entire consortium, such as the BATTERY 2030+, a consortium accelerating advanced battery technologies. Uploaded data and metadata are controlled via fine grained permissions, allowing access to individual project members or the full initiative. The formalized upload process ensures data are formatted and ready for publication in open repositories when needed. This paper reviews the repository's key features, showing how the BIG-MAP Archive enables secure, controlled data sharing within large consortia. It ensures data confidentiality while supporting flexible, permissions-based access and can be easily redeployed for other consortia, including MaterialsCommons4.eu and RAISE (Resource for AI Science in Europe).

cs.DB↗

arXiv2025

Predicting aqueous and electrochemical stability of 2D materials from extended Pourbaix analyses

A key challenge for computational discovery of electrocatalytic materials is the reliable prediction of thermodynamic stability in aqueous environment and under different electrochemical conditions. In this work, we first evaluate the electrochemical stability of more than 3000 two-dimensional (2D) materials using conventional Pourbaix diagrams (CPDs). Due to the complete neglect of thermodynamic barriers along the (often complex) reaction pathways, the vast majority of the materials are predicted to be unstable even though some are known to be stable in practice. We then introduce an analysis based on the surface Pourbaix diagram (SPD) including 'early intermediate states' that represent the first steps of the key surface passivation and dissolution reactions. The SPD framework is applied to the 2D materials MoS$_2$, phosphorene, and the MXene Ti$_2$C, all of which are predicted to be unstable by the CPD. For MoS$_2$, our approach reproduces the experimental pH-U stability window as well as the experimental desulphurization potential. For phosphorene and Ti2$_C$, the SPD approach is used to investigate the spontaneous degradation mechanism and the potential-dependent surface termination, respectively, again yielding good agreement with experiments. The SPD-based stability analysis emerges as a versatile and quantitative method for prediction of stability and investigation of surface structures in electrochemical environments.

cond-mat.mtrl-sci↗

arXiv2025

Atomic-scale observation of $d$-$\pi$-$d$ spin coupling in coordination structures

Spin coupling between magnetic metal atoms and organic radicals plays a pivotal role in high-performance magnetic materials. The complex interaction involving multi-spin centers in bulk materials makes it challenging to study spin coupling at the atomic scale. Here, we investigate the $d$-$\pi$-$d$ spin interaction in well-defined metal-organic coordinated structures composed of two iron (Fe) atoms and four all-trans retinoic acid (ReA) molecules, using low-temperature scanning tunneling microscopy and atomic force microscopy. The ReA molecule is turned into a spin-$1/2$ radical state by dehydrogenation, facilitating strong magnetic coupling with the coordinated Fe atoms. Comprehensive theoretical analysis, based on density functional theory and valence bond theory, further elucidates the intrinsic mechanism of ferrimagnetic spin coupling in the coordination structure. Specifically, simultaneous antiferromagnetic coupling of Fe dimer to ReA radicals parallelizes the dimer spin orientation. This work contributes to the fundamental understanding of spin interaction in metal-organic coordination structures and provides microscopic insights for designing advanced magnetic materials.

cond-mat.mtrl-sci↗

arXiv2022

Observation of biradical spin coupling through hydrogen bonds

Investigation of intermolecular electron spin interaction is of fundamental importance in both science and technology.Here, radical pairs of all-trans retinoic acid molecules on Au(111) are created using an ultra-low temperature scanning tunneling microscope. Antiferromagnetic coupling between two radicals is identified by magnetic-field dependent spectroscopy.The measured exchange energies are from 0.1 to 1.0 meV. The biradical spin coupling is mediated through O-H$\cdots$O hydrogen bonds, as elucidated from analysis combining density functional theory calculation and a modern version of valence bond theory.

cond-mat.mes-hall↗

arXiv2021

Data Management Plans: the Importance of Data Management in the BIG-MAP Project

Open access to research data is increasingly important for accelerating research. Grant authorities therefore request detailed plans for how data is managed in the projects they finance. We have recently developed such a plan for the EU-H2020 BIG-MAP project - a cross-disciplinary project targeting disruptive battery-material discoveries. Essential for reaching the goal is extensive sharing of research data across scales, disciplines and stakeholders, not limited to BIG-MAP and the European BATTERY 2030+ initiative but within the entire battery community. The key challenges faced in developing the data management plan for such a large and complex project were to generate an overview of the enormous amount of data that will be produced, to build an understanding of the data flow within the project and to agree on a roadmap for making all data FAIR. This paper describes the process we followed and how we structured the plan.

cond-mat.mtrl-sci↗

arXiv2021

Automatic diffusion path exploration for multivalent battery cathodes using geometrical descriptors

Stable and fast ionic conductors for magnesium cathode materials have the prospect of enabling high energy density batteries beyond current Lithium-ion technologies. So far, only a few candidate materials have been identified leading to data only being scarcely available to the community. Here, we present a systematic study, in the framework of Density Functional Theory, including the estimation of the diffusion barrier for 16 materials through employing Nudged Elastic Band (NEB) calculations. By introducing a path finder algorithm based on the idea of Voronoi tessellations, we show that an estimate of the transition state configuration can be extracted automatically prior to running NEB-calculations. Using geometrical descriptors in combination with a principal component analysis it is possible to further sub-group the diffusion paths. This approach also extends to materials which are not part of the study, making it a viable approach to more efficiently explore crystal structures with distinguishable diffusion characteristics.

cond-mat.mtrl-sci↗

arXiv2021

Atomic-scale insights into electro-steric substitutional chemistry of cerium oxide

Cerium oxide (ceria, CeO2) is one of the most promising mixed ionic and electronic conducting materials. Previous atomistic analysis has covered widely the effects of substitution on oxygen vacancy migration. However, an in-depth analysis of the role of cation substitution beyond trivalent cations has rarely been explored. Here, we investigate soluble monovalent, divalent, trivalent and tetravalent cation substituents. By combining classical simulations and quantum mechanical calculations, we provide an insight into defect association energies between substituent cations and oxygen vacancies as well as their effects on the diffusion mechanisms. Our simulations indicate that oxygen ionic diffusivity of subvalent cation-substituted systems follows the order Gd>Ca>Na. With the same charge, a larger size mismatch with Ce cation yields a lower oxygen ionic diffusivity, i.e., Na>K, Ca>Ni, Gd>Al. Based on these trends, we identify species that could tune the oxygen ionic diffusivity: we estimate that the optimum oxygen vacancy concentration for achieving fast oxygen ionic transport is 2.5% for GdxCe1-xO2-x/2, CaxCe1-xO2-x and NaxCe1-xO2-3x/2 at 800 K. Remarkably, such a concentration is not constant and shifts gradually to higher values as the temperature is increased. We find that co-substitutions can enhance the impact of the single substitutions beyond that expected by their simple addition. Furthermore, we identify preferential oxygen ion migration pathways, which illustrate the electro-steric effects of substituent cations in determining the energy barrier of oxygen ion migration. Such fundamental insights into the factors that govern the oxygen diffusion coefficient and migration energy would enable design criteria to be defined for tuning the ionic properties of the material, e.g., by co-doping.

cond-mat.mtrl-sci↗

arXiv2020

Oxygen Evolution Reaction on Perovskites: A Multieffect Descriptor Study Combining Experimental and Theoretical Methods

The correlation between ex situ electronic conductivity, oxygen vacancy content, flat-band potential (Efb), and the oxygen evolution reaction (OER) activity for a wide range of perovskite compositions are investigated experimentally and theoretically. It is found that all of these parameters can affect the OER activity; however, none of them alone play a crucial role in determining the electrocatalytic activity. The correlation of one single physicochemical property with the OER activity always presents deviation points, indicating that a limitation does exist for such 2-dimensional correlations. Nevertheless, these deviations can be explained considering other physicochemical properties and their correlation with the OER activity. Hence, this work aims in simultaneously linking the OER activity with several physicochemical materials properties. The concept of the OER/multidescriptor relationship represents a significant advancement in the search and design of highly active oxygen evolution catalysts, in the quest for efficient anodes in water electrolyzers.

cond-mat.mtrl-sci↗

arXiv2020

Structural and chemical mechanisms governing stability of inorganic Janus nanotubes

One-dimensional inorganic nanotubes hold promise for technological applications due to their distinct physical/chemical properties, but so far advancements have been hampered by difficulties in producing single-wall nanotubes with a well-defined radius. In this work we investigate, based on Density Functional Theory (DFT), the formation mechanism of 135 different inorganic nanotubes formed by the intrinsic self-rolling driving force found in asymmetric 2D Janus sheets. We show that for isovalent Janus sheets, the lattice mismatch between inner and outer atomic layers is the driving force behind the nanotube formation, while in the non-isovalent case it is governed by the difference in chemical bond strength of the inner and outer layer leading to steric effects. From our pool of candidate structures we have identified more than 100 tubes with a preferred radius below 35 Å, which we hypothesize can display unique properties compared to their parent 2D monolayers. Simple descriptors have been identified to accelerate the discovery of small-radius tubes and a Bayesian regression approach has been implemented to assess the uncertainty in our predictions on the radius.

cond-mat.mtrl-sci↗

arXiv2020

Two-dimensional materials from high-throughput computational exfoliation of experimentally known compounds

We search for novel two-dimensional materials that can be easily exfoliated from their parent compounds. Starting from 108423 unique, experimentally known three-dimensional compounds we identify a subset of 5619 that appear layered according to robust geometric and bonding criteria. High-throughput calculations using van-der-Waals density-functional theory, validated against experimental structural data and calculated random-phase-approximation binding energies, allow to identify 1825 compounds that are either easily or potentially exfoliable, including all that are commonly exfoliated experimentally. In particular, the subset of 1036 easily exfoliable cases---layered materials held together mostly by dispersion interactions and with binding energies up to $30-35$ meV$\cdot\textÅ^{-2}$---provides a wealth of novel structural prototypes and simple ternary compounds, and a large portfolio to search materials for optimal properties. For the 258 compounds with up to 6 atoms per primitive cell we comprehensively explore vibrational, electronic, magnetic, and topological properties, identifying in particular 56 ferromagnetic and antiferromagnetic systems, including half-metals and half-semiconductors.

cond-mat.mtrl-sci↗

arXiv2019

Yttrium Tantalum Oxynitride Multiphases as Photoanodes for Water Oxidation

Perovskite yttrium tantalum oxynitride is theoretically proposed as a promising semiconductor for solar water splitting because of the predicted bandgap and energy positions of band edges. In experiment, however, we show here that depending on processing parameters, yttrium tantalum oxynitrides exist in multiphases, including the desired perovskite YTaON2, defect fluorite YTa(O,N,o)4, and N-doped YTaO4. These multiphases have bandgaps ranging between 2.13 and 2.31 eV, all responsive to visible light. The N-doped YTaO4, perovskite main phase, and fluorite main phase derived from crystalline fergusonite oxide precursors exhibit interesting photoelectrochemical performances for water oxidation, while the defect fluorite derived from low crystallized scheelite-type oxide precursors show negligible activity. Preliminarily measurements show that loading IrOx cocatalyst on N-doped YTaO4 significantly improves its photoelectrochemical performance encouraging further studies to optimize this new material for solar fuel production.

physics.app-ph↗

arXiv2019

Towards Photoferroic Materials by Design: Recent Progresses and Perspective

The use of photoferroic materials that combine ferroelectric and light harvesting properties in a photovoltaic device is a promising route to significantly improve the efficiency of solar cells. These materials do not require the formation of a p-n junction and can produce photovoltages well above the value of the band gap, because of the spontaneous intrinsic polarization and the formation of domain walls. In this perspective, we discuss the recent experimental progresses and challenges for the synthesis of these materials and the theoretical discovery of novel photoferroic materials using a high-throughput approach.

cond-mat.mtrl-sci↗

arXiv2019

Anisotropic Proton and Oxygen Ion Conductivity in Epitaxial Ba2In2O5 Thin Films

Solid oxide oxygen ion and proton conductors are a highly important class of materials for renewable energy conversion devices like solid oxide fuel cells. Ba2In2O5 (BIO) exhibits both oxygen ion and proton conduction, in dry and humid environment, respectively. In dry environment, the brownmillerite crystal structure of BIO exhibits an ordered oxygen ion sublattice, which has been speculated to result in anisotropic oxygen ion conduction. The hydrated structure of BIO, however, resembles a perovskite and the protons in it were predicted to be ordered in layers. To complement the significant theoretical and experimental efforts recently reported on the potentially anisotropic conductive properties in BIO, we measure here the proton and oxygen ion conductivity along different crystallographic directions. Using epitaxial thin films with different crystallographic orientations the charge transport for both charge carriers is shown to be anisotropic. The anisotropy of the oxygen ion conduction can indeed be explained through the layered structure of the oxygen sublattice in brownmillerite BIO. The anisotropic proton conduction however, further supports the suggested ordering of the protonic defects in the material. The differences in proton conduction along different crystallographic directions attributed to proton ordering in BIO are of a similar extent as those observed along different crystallographic directions in materials where proton ordering is not present but where protons find preferential conduction pathways through chain-like or layered structures.

cond-mat.mtrl-sci↗

arXiv2019

Determination of conduction and valence band electronic structure of LaTiOxNy thin film

The nitrogen substitution into the oxygen sites of several oxide materials leads to a reduction of the band gap to the visible light energy range, which makes these oxynitride semiconductors potential photocatalysts for efficient solar water splitting. Oxynitrides typically show a different crystal structure compare to the pristine oxide material. Since the band gap is correlated to both the chemical composition and the crystal structure, it is not trivial to distinguish what modifications of the electronic structure induced by the nitrogen substitution are related to compositional and/or structural effects. Here, X-ray emission and absorption spectroscopy is used to investigate the electronic structures of orthorhombic perovskite LaTiOxNy thin films in comparison with films of the pristine oxide LaTiOx with similar orthorhombic structure and cationic oxidation state. Experiment and theory show the expected upward shift in energy of the valence band maximum that reduces the band gap as a consequence of the nitrogen incorporation. But this study also shows that the conduction band minimum, typically considered almost unaffected by the nitrogen substitution, undergoes a significant downward shift in energy. For a rational design of oxynitride photocatalysts the observed changes of both the unoccupied and occupied electronic states have to be taken into account to justify the total band gap narrowing induced by the nitrogen incorporation.

cond-mat.mtrl-sci↗